TWI242689B - Chemically amplified negative photoresist composition for the formation of thick films, photoresist base material and method of forming bumps using the same - Google Patents

Abstract

The present invention provides a chemically amplified negative photoresist composition for thick films having high sensitivity and good plating resistance and suitable for the formation of thick films favorable for use as materials for forming bumps, re-wiring and a metal post used in a CSP manufacturing technique and to provide a photoresist base material and a method for forming bumps using the same. In details, the chemically amplified negative photoresist composition for the formation of thick films having a thickness of 20 to 150 mum includes (A) an alkali-soluble resin, (B) a compound which generates an acid upon irradiation with active light or radiant ray, and (C) a compound which serves as a crosslinking agent in the presence of an acid. The alkali-soluble resin (A) includes (a) a novolak resin having a weight average molecular weight of from 5000 to 10000, and (b) a polymer containing at least a hydroxystyrene constitutional unit and having a weight average molecular weight of less than or equal to 5000.

Description

1242689 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __ _B7_ V. Description of Invention (彳) [Technical Field of the Invention] The present invention relates to a chemically amplified negative photoresist composition for thick films, a photoresist substrate, and the use thereof Method of forming bumps. In detail, the present invention relates to bump formation, wiring formation, and metal pillars (semiconductor formation) performed when a semiconductor or electronic component represented by a CSP (chip size package) is mounted on a circuit substrate. Metal post) Chemically amplified negative photoresist composition for thick films that can be used for photofabrication in the formation, interlayer insulation layer, circuit protection film, and precision component processing and manufacturing. . [Incoming technology] Optoelectronic processing is to apply a photosensitive resin composition on the surface of the processed object, and apply patterning to the coating film according to photolithography technology. Use this as a mask and use Chemical uranium engraving, electrolytic uranium engraving or electroplating as the main body of electroforming (electroforming) technology alone or in combination to produce a variety of precision parts of the general term, has become the current precision micro-machining technology mainstream. In recent years, with the down-sizing of electronic equipment, the high-density mounting technology of LSI (Large Integrated Circuits) has been advanced, and it is hoped to achieve multi-pin film mounting and package size based on LSI. ) 'S miniaturization, flip-chip (two-dimensional mounting technology) and three-dimensional mounting technology upgrade. In terms of such high-density mounting technology, the terminals themselves are bumps for connection terminals called bumps with a height of more than 20 // m, and the paper size from the peripheral terminals on the wafer to the mounted terminals. Applicable to China National Standard (CNS) A4 specification (21〇 > < 297mm) (Please read the notes on the back before filling this page)

-4- 1242689 A7 B7 Fifth, the rewiring at the position of the invention description (2), ultra-thick film wiring called metal pillar, etc., must be arranged on the substrate with high precision. In the future, it will correspond to further LSI With its miniaturization, the requirements for high-density mounting technology will become higher and higher. As a material used in the manufacturing of such a component or the formation of an IC (integrated circuit) bump, a thick film photoresist can be used. In addition, the thick film referred to here means a thickness of 20 to 15 0 // m. Such a thick film is, for example, using the thick film pattern as a mask, and it can be used to form bumps or metal pillars according to the plating process, to form lead frames according to the metal etching process, to dry etch ( dry etching). For example, Japanese Patent Laid-Open Publication No. 10-200075, Japanese Patent Laid-Open Publication Nos. 2000-0-3997, and Japanese Patent Laid-Open Publication Nos. 2000-66386 are described as useful for bump formation. Or a photosensitive resin composition for thick film for wiring formation. However, since these conventional thick film photosensitive resin compositions are thick films, if the photoresist film is to be fully reacted over the entire area, a large amount of reaction initiator is required. However, when the reaction initiator is used in a large amount, the compatibility tends to deteriorate or the storage stability tends to decrease. Therefore, the development of a high-sensitivity reaction initiator is desired. On the other hand, as a photosensitive resin composition having a high sensitivity, a chemically amplified resist film using an acid generator is known. The optically amplified photoresist is characterized in that protonic acid (protonacid) generated from an acid generator contained in the component due to radiation irradiation will cause acid contact with alkaline resins in the resin composition due to heat treatment after exposure. MEDIA REACTION. In this way, the photoresponse efficiency (response to each photon) is lower than the original resistance of this paper. The Chinese paper standard (CNS) A4 specification (210X29 < 7 mm) applies (Please read the note on the back first) Please fill in this page for further information) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 1242689 A7 ______B7___ V. Invention Description (3) (Please read the precautions on the back before filling this page) The etching film is to achieve breakthrough High sensitivity. Examples of typical chemically-amplified negative resist films include LE in SPIE (Proceeding 〇f SPIE) Annual Report, Volume 1086, Pages 34-47 (1889) Bogan et al. Combined a resist film of polyvinyl phenol and a melamine derivative. However, when these chemically amplified photoresists are used to form a thick film, cracks occur and the required plating resistance cannot be obtained. In addition, when the existing thick film is exposed with a photoresist, it is preferable that the exposure portion is in contact with the uranium-resistant film (resist) due to problems such as light diffusion during the exposure. However, proximity exposure (gap exposure) with a gap between the exposed portion and the resist film portion is more advantageous in the manufacturing process and in its exposure method, and it also requires a thick film resist with sufficient performance. Development of membranes. [Problems to be Solved by the Invention] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Therefore, the purpose of the present invention is to solve the problems of the prior art mentioned above, and to improve the sensitivity and plating resistance, and it is suitable as a bump. , Redistribution, metal pillar forming material, or CSP (Controlled Surface Porosity) material, a thick film formed by a thick film, a chemically amplified negative photoresist composition for a thick film, a photoresist substrate, and a projection using the same Block method. [Means to Solve the Problem] The invention in item 1 of the scope of the patent application contains (A) an alkali-soluble resin, (B) a compound that will generate an acid due to radiation, and the paper size is subject to Chinese national standards (CNS ) A4 specification (210X297 mm) " -6- 1242689 A7 B7 V. Description of the invention (4) (Please read the precautions on the back before filling this page) Cross-linking reaction in the presence of (C) acid The chemically amplified negative photoresist composition of the compound is characterized in that the aforementioned (A) component is composed of (a) a phenol wake-up lacquer resin having a weight-average molecular weight in a range of 5000 to 1000, and (B) A chemically amplified negative photoresist composition for thick films made of a mixture of polymers having at least hydroxystyrene structural units and a weight average molecular weight of 5000 or less. The invention in item 2 of the scope of patent application is in the chemically amplified negative photoresist composition for thick film described in item 1 of the scope of patent application, which is characterized by (a) the component in the presence of an acid catalyst Next, a m-cresol novolak resin obtained by condensing m-cresol with an acid. The invention in item 3 of the scope of patent application is in the chemically amplified negative photoresist composition for thick film described in item 1 of the scope of patent application, and is characterized in that in the (A) component, if (a) When the total of the ingredient and (b) ingredients is 100 parts by weight, (a) the ingredient is 50 to 98 parts by weight, and (b) the ingredient is 50 to 2 parts by weight. The invention of item 4 of the scope of patent application printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is in the chemically amplified negative photoresist composition for thick film described in item 1 of the scope of patent application, which is characterized by: (B ) Ingredients are at least two sulfonic acid oxime groups represented by the general formula R—S0022—N = C (CN) — (where R is a substituted or unsubstituted alkyl or aryl group) Compounds. The invention in item 5 of the scope of patent application is in the chemically amplified negative photoresist composition for thick films described in item 4 of the scope of patent application, and is characterized by (B) ingredients, which can be used in general paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1242689 Μ ___ B7 V. Description of the invention (5)

RS〇2〇-N = C (CN)-AC (CN) = N-0S02-R (Please read the notes on the back before filling this page) (where A is a binary organic group and R is Substituted or unsubstituted alkyl or aryl). The invention in the sixth scope of the patent application belongs to the chemically amplified negative photoresist composition for thick films in the fifth scope of the patent application, which is characterized in that a in the general formula of the component (B) is benzene And R are lower alkyl. The invention of item 7 in the scope of patent application is in the chemically amplified negative photoresist composition for thick film used in item 1 of the scope of patent application, which is characterized by: (A) component, (B) component and (C) ) When the total of the ingredients is 100 parts by weight, the (B) ingredient is from 0.1 to 1 part by weight. The invention of the eighth patent application is a photoresist substrate, which is a negative photoresist layer substrate having a substrate and a negative photoresist layer provided on the substrate, and is characterized by the aforementioned negative photoresist The layer is made of a chemically amplified negative photoresist composition for thick films as described in any one of items 1 to 7 of the scope of patent application, and has a film thickness of 20 to 150. The invention of the 9th item of the patent application scope printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economics is a bump formation method, which is characterized in that the substrates of the electronic components are coated with the first to the 7th patent application scope. The chemically amplified negative photoresist composition for a thick film according to any one of the foregoing, and sequentially applying selective exposure, heat treatment, and phase development treatment to the obtained coating film to form a negative resist film pattern, The resist pattern is used as a mask for plating. [Implementation form of the invention] This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -8-1242689 Α7

V. Description of the invention (6) (Please read the precautions on the back before filling in this page) The inventors and others have done their best to study the results and understand the fact that the characteristics required for the refractory film will change due to the type of plating solution. By optimizing its constituent elements, the aforementioned problems are solved, and it has been found that a chemically amplified negative photoresist composition for thick films is particularly useful in the process of solder plating and copper plating. Hereinafter, the composition of the present invention will be described. (A) The alkali-soluble resin (A) is composed of (a) a phenolic lacquer resin having a weight average molecular weight in the range of 5000 to 10,000, and (b) a weight average molecular weight having at least a hydrogen-based ethyl structure. Alkali-soluble resin made from a mixture of polymers up to 5,000. (a) Phenolic resins printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (a) Phenolic resins used in the present invention are composed of, for example, aromatic compounds having phenolic hydroxyl groups (hereinafter, simply referred to as" phenols ") and aldehydes. It is prepared by addition and condensation under acid catalyst. Examples of phenols that can be used at this time include phenylhydrazone, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol , P-butylphenol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5 — Xylenol, 2, 3, 5-trimethylphenol, 3, 4, 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone-methyl ether, gallophenol, m-phenol Pyrogallols, hydroxydiphenols, bisphenol A, gallic acid, gallic acid esters, α-naphthol, pyrene-naphthol and the like. In addition, aldehydes can be exemplified: the formaldehyde of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -9- 1242689 A7 _ B7 V. Description of the invention (7) (Please read the precautions on the back before (Fill in this page), paraldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. The catalyst used in the addition condensation reaction is not limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid can be used for the acid catalyst. (a) The weight-average molecular weight of the alkali-soluble phenolic lacquer resin is preferably from 5,000 to 1,000. In addition, if it is a m-cresol novolak resin obtained by condensing m-cresol with aldehydes, it is particularly suitable as a chemically amplified negative photoresist composition for thick films. (b) Polymer having hydroxystyrene structural unit The component (b) used in the present invention may be exemplified by a polymer having at least a hydroxystyrene structural unit. The polymer printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics can be exemplified by: hydroxystyrene such as p-hydroxystyrene; α-alkyl such as α-fluorenylhydroxystyrene and α-ethylhydroxystyrene Free radical polymer or ionic polymer of hydroxystyrene monomer; for example, a combination of hydroxystyrene structural units such as hydroxystyrene, α-alkylhydroxystyrene and other structural units other than the aforementioned hydroxystyrene structural units polymer. Among the monomers other than the above-mentioned hydroxystyrene structural unit, preferred are monomers in which the hydroxyl group of hydroxystyrene is replaced with another group, or monomers having an α, / 3-unsaturated double bond, and the like. In order to replace other groups of the hydroxyl group of the aforementioned hydroxystyrene, an alkali dissolution inhibiting group which does not dissociate by an acid may be used. Examples of the aforementioned alkali dissolution inhibiting group include: substituted or unsubstituted benzenesulfonyloxy, substituted or unsubstituted naphthylsulfonyloxy, substituted or unsubstituted phenylcarbonylsulfonyloxy, and substituted or unsubstituted naphthylcarbonylsulfonyl In the specific examples of substituted or unsubstituted benzenesulfonyloxy, benzenesulfonyloxy, chlorobenzenesulfonyloxy, toluene, etc. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) -10- 1242689 A7 __ B7 V. Description of the Invention (8) Sulfamethyloxy, ethylbenzenesulfonyloxy, propylbenzenesulfonyloxy, methoxybenzenesulfonyl hydrazine, ethoxybenzenesulfonyl Fluorenyloxy, propoxybenzenesulfonyloxy, acetaminophensulfonyl, etc .; in the specific examples of substituted or unsubstituted naphthalenesulfonyloxy, naphthalene_fluorenyloxy, chloronaphthalenesulfonyloxy , Methylnaphthylsulfonyloxy, ethylnaphthylsulfonyloxy, cypernaphthylsulfonyloxy, methoxynaphthylsulfonyloxy, ethoxylnaphthylsulfonyloxy, propoxycymsulfonyloxy, acetamidine Sulfur oxygen. Further, examples of the substituted or unsubstituted phenylcarbonylfluorenyloxy group and the substituted or unsubstituted naphthalenecarbonylfluorenyloxy group include those in which the aforementioned substituted or unsubstituted sulfonyloxy group is substituted with a carbonylfluorenyloxy group. Among them, acetamidosulfonyloxy or acetamidinylsulfonyloxy is preferred. Specific examples of the monomer having an α, / 3 -unsaturated double bond include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and styrene such as α-methylstyrene. Styrene-based monomers, acrylic acid monomers such as methyl acrylate, methyl methacrylate, and phenyl methacrylate; vinyl acetate-based monomers such as vinyl acetate and vinyl benzoate; but styrene is preferred. Poly (4-hydroxystyryl-styrene), poly (4-hydroxystyryl-methylstyrene) copolymers made from hydroxystyrene and styrene, etc. It is better because of its high heat resistance. The component (b) has a weight-average molecular weight of 5,000 or less, and preferably 4,000 or less. If the weight-average molecular weight exceeds 50 000, the phase dissolving power will be significantly reduced. Here, in the (A) component, if the sum of the (a) component and the (b) component is 100 parts by weight, the (A) component is 50 to 98 parts by weight, preferably 55 to 95. Parts by weight, (b) 50 to 2 The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X29 < 7 mm 1 ~~ " -11-f Please read the precautions on the back before filling in this page} --= Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1242689 A7 __ B7 V. Description of the invention (9) parts by weight, preferably 4 5 to 5 parts by weight. Such a proportion, especially for thick films The chemically amplified negative photoresist composition is suitable. (Please read the precautions on the back before filling out this page) (B) Compounds that generate acid due to radiation exposure (B) component acid generator used in the present invention,祗 The compound that produces acid directly or indirectly due to acid is not particularly limited, but it can be specifically exemplified: 2, 4—bis (trichloromethyl) -6— [2- (2-furanyl) ethynyl] —Second triazine, 2 — 4 —bis (trichloromethyl) _6- [2-(5-methyl-1—furanyl) ethylidene] Second triazine, 2, 4-bis (trichloromethyl) -6— [2- (5-methyl-2-furanyl) ethynyl] —second triazine, 2, 4-bis (tri Chloromethyl) — 6-[2- (5-propyl-2-furanyl) ethylidene] — 2nd triazine, 2, 4 —bis (trichloromethyl) —6 — [2— (3 , 5-dimethoxyphenyl) ethylidene] -second triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethylidene 〕 —Second triazine, 2, 4 —bis (trichloromethyl) —6-[2 — (3, 5 — Dipropoxyphenyl) ethoxyl printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs] 1 Second triazine, 2,4- (trichloromethyl) -6 — [2 — (3-methoxy-5—ethoxyphenyl) ethynyl] — second triazine, 2, 4 —bis (Trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethynyl] -second triazine, 2, 4, bis (trichloromethyl) -6- [2- (3,4-monomethylenedioxyphenyl) ethylidene] -second triazine, 2,4-bis (trichloromethyl) -6- (3,4-monomethylenedioxy Phenyl ） —Second triazine, 2,4 bis (trichloromethyl) -6— (3-bromo-4—methoxy) phenyl—The first paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) -12- 1242689

A7 B7

Description 10 ^ m. 2,4-bis (trichloromethyl) -6- (2-bromo- 4 2oxy) phenyl-second triazine, 2,4-bis (trichloromethyl) Mono (2-bromo- 4-methoxy) styrylphenyl-second triazine, 4-bis (trichloromethyl) -6- (3-bromo-4-methoxy-4 (yl 1st toluene vinylphenyl-second triazine, 2- (4- 6-bis (trichloromethyl)-1, 3, 5-trioxonaphthyl) -4, 6-bis (trichloromethyl) ) —1,3,5 —, 2- [2- (2-furanyl) ethylidene] methoxyphenyl), 2— (4 4, 6—bischloromethyl) 1, 3, 5 —Triazine, 2 — [2 -— (5-methyl 2 -.sulfanyl) ethylidene] —4, 6-bis (trichloromethyl) — 3, 5-triazine, 2 — [2 — ( 3, 5 —dimethoxyphenyl) (Please read the precautions on the back before filling out this page) ··································································· 2-Bis 2-5-trisyl]-4, 6-Bis (trichloromethyl)-1, Mono- [2- (3,4-dimethoxyphenyl) ethoxy (trichloromethyl) -1,3,5-triazine, 2-yldioxyphenyl)-[4,6-bis (trichloromethyl) Triazine, (1,3-dibromopropyl) -1,2,3-dibromopropyl) -1,3,5 — Printed triazine compounds and reference compounds (2, 3- Dibromopropyl) a halogen-containing triazine compound represented by the following general formula; 3,5-triazinyl] -4,6--6- (3,4-)-1,3,3,5-triazinetriazine Customizable halogenated isocyanates, etc.

(In the formula, R1 to R3 indicate that the basic paper size of halogenated institutes can be the same or different. Applicable to China National Standard (CNS) A4 specification (210X 297 male diamond) -13- 1242689 A7 —B7 V. Description of the invention (M)) (Please read the precautions on the back before filling this page) ^ One (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzene_fluorenimino) -1,2,4-dichlorophenyl Acetonitrile, ^ (benzenesulfonyloxyimino) -2,6 dichlorophenylacetonitrile, α- (benzenesulfonyloxyiminoyl) -2,6-dichlorophenylacetonitrile, α- ( 2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonamidooxyimino) > ~ 1-cyclopentenylacetonitrile, etc. can be represented by the following general formula Compound

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R4 represents a monovalent to trivalent organic group, R5 represents a substituted ^ $ substituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group, and m η represents 1 to The natural number of 3. Here, the aromatic compound group refers to a group of compounds showing physical and chemical properties peculiar to aromatic compounds, and may include aromatic hydrocarbon groups such as phenyl, naphthyl, furanyl, and thiophene. These groups may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. In addition, R5 is particularly preferably an alkyl group having 1 to 4 carbon atoms, Methyl, ethyl, propyl, and butyl are exemplified. Compounds in which R4 is an aromatic compound group and R5 is a lower alkyl group are particularly preferred. For an acid generator represented by the general formula, η = 1 When R4 is any of phenyl, tolyl, and methoxyphenyl, and R5 is a methyl compound, specific examples include α- (methylsulfonyloxyimino) -1 -phenylacetonitrile, ^ Mono (methanesulfonyloxyimino) -1 (p-tolyl) acetonitrile, α- (methylsulfonyloxyimino) 1— (p-methoxyphenyl) acetonitrile. When η = 2, the Chinese paper standard (CNS) A4 specification (210 > < 297 mm 1 -14-1242689 A7 B7) can be applied to the above paper size. (12) As the acid generator represented by the general formula, specifically, the acid generator represented by the following chemical formula may be mentioned.)

H3C—S—〇 一 N = C— \ y—C == NΟ—S—CH3 ° 2 Ϊν Ν ^ = / ^ Jn ° 2 (Please read the notes on the back before filling this page) Intellectual Property Bureau, Ministry of Economic Affairs Printed by employee consumer cooperatives C2H5—S—〇N = C— \ 一 O 一 S * ~~~ C2H5 〇2 iN… Cx | Hg ~ S—〇—N = C— \ C = N—O—S— 〇 z Jn Nv = > ^ Jn 〇2 bis (p-toluenesulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diamine Bissulfonyldiazomethane, such as azomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane; p-tolylsulfonic acid 2-nitrobenzyl, p-tolylsulfonic acid 2 , 6-dinitrobenzyl, nitrobenzyltosylsulfonate, dinitrobenzyltosylsulfonate, nitrobenzylsulfonate, nitrobenzylcarboxylic acid ester, dinitrobenzylcarboxylic acid Nitrobenzyl derivatives such as esters; gallophenol trimethylsulfonate, gallophenol trimethylsulfonate, benzyltoluenesulfonate, benzylsulfonate, N-methylsulfonoxopiprazine, N-Trichloromethanesulfonyloxoperoxamine imine This paper is sized for China National Standard (CNS) A4 (21 0X 297 mm) -15- 1242689 A7 __B7 V. Description of the invention (13) (Please read the precautions on the back before filling this page), N-phenylsulfonyloxymaleimide, N-methylsulfonium Sulfonates such as oxophthalophthalimide; trichloromethane sulfonates such as N-hydroxyphthalocyanine imine, N-hydroxyphthalocyanine; etc .; Oxyphenyl) phenyl iodotrifluoromethanesulfonate, bis (p-tert-butylphenyl) iodofluorene trifluoromethanesulfonate, triphenylphosphonium hexafluorophosphate, (4-methoxyphenyl ) Iron salts of diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, etc .; benzoin tosylate, α-methyl benzosulfonyl tosylate Benzoin tosylsulfonium salts such as salts; other diphenyl iron iodonium salts, triphenylphosphonium salts, phenyldiazonium salts, benzyl carboxylic acid esters, and the like. Among the foregoing, as the (B) component, there are at least two general formulas R—S〇2〇—N = C (CN) — (where R is substituted or unsubstituted, for example, carbon number 1 to 8) Alkyl or aryl) sulfonic acid oxime-based compounds, in particular, can be printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R-S〇2〇-N ^ C (CN) —A — C (CN ) = N —〇S〇2 — R (wherein A is a divalent alkylene or aromatic compound group having 1 to 8 carbon atoms, such as substituted or unsubstituted, and R is a substituted or unsubstituted carbon group, such as carbon A compound represented by an alkyl group or an aryl group of 1 to 8 is preferred. Here, the aromatic compound group refers to a group of compounds exhibiting physical and chemical properties peculiar to aromatic compounds, such as aromatic hydrocarbon groups such as phenyl and naphthyl, and heterocyclic groups such as furyl and thienyl. These groups may have more than one appropriate substituent on the ring, for example, & 's scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm)' ~ -16- 1242689 A7 _ B7 ___ V. Description of the invention (14) A halogen atom, an alkyl group, an alkoxy group, a nitro group, and the like. Furthermore, in the general formula described above, A is phenylene, and R is, for example, a lower alkyl group having 1 to 4 carbon atoms. (Please read the notes on the back before filling this page) Here, the aforementioned (B) component can be 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight based on the total of (A) to (C) components Range of shares. If the component (B) is less than 0.01 parts by weight, the plating resistance, chemical resistance, and adhesion of the thick film obtained due to insufficient crosslinking and curing caused by heat and light may be reduced, resulting in The shape of the bumps may be poor and unfavorable. If it exceeds 5 parts by weight, it may be unfavorable when the appearance is poor. In particular, if the chemically amplified negative photoresist composition for thick films contains the component (B) in the range of 0.1 to 1 part by weight, it is better to obtain a balance of various characteristics of the composition. (C) Compounds that undergo a cross-linking reaction in the presence of an acid The (C) component (cross-linking agent) used in the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs may be a well-known cross-linking agent. Use of amine compounds such as melamine resins, urea resins, guanamine resins, glycol urea-formaldehyde resins, succinamide-formaldehyde resins, ethylene urea-formaldehyde resins, among which methoxymethylated melamine resins or methoxymethyl Alkoxymethylated amine-based resins such as urea-based resins are preferably used. The aforementioned alkoxymethylated amine-based resin is a condensate obtained by reacting melamine or urea with formaldehyde water in a boiling aqueous solution, and using a lower alcohol such as methanol, ethanol, propanol, butanol, isopropanol, etc. It can be produced by etherifying the reaction solution, and then cooling the reaction solution to cause precipitation. Specific examples of the aforementioned alkoxymethylated amine-based resin include methoxymethylated melamine resin and ethoxymethyl. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 1242689 A7 __B7 5 、 Explanation of invention (15) (Please read the precautions on the back before filling in this page) Basic melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxylate Methylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin, and the like. These alkoxymethylated amine-based resins may be used alone or in combination of two or more. In particular, an alkoxymethylated melamine resin is preferable because it can form a stable resist film pattern with a small change in the size of the resist film pattern with a change in the amount of radiation exposure. Among them, a methoxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin, and a butoxymethylated melamine resin are preferred. The aforementioned (C) component may contain a range of 1 to 30 parts by weight based on 100 parts by weight of the total of (A) to (C) components. If the component (C) is less than 1 part by weight, the resulting thick film may have reduced plating resistance, chemical resistance, and adhesion, or the shape of the formed bump may be poor and unfavorable, such as more than 30 parts by weight It is not appropriate to have poor appearance during the appearance. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, the chemically amplified negative photoresist composition for thick films of the present invention is suitable for viscosity adjustment and can be appropriately equipped with an organic solvent. Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol. Dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Alcohol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethyl ether Glycol monobutyl ether acetate, B paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -18-1242689 A7 ___ B7 · V. Description of the invention (16) Glycol monophenyl ether acetate , Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monobenzene Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate 3-methoxybutylacetate, 4-methoxybutylacetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl Methyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2 ~ methyl-3-methoxypentyl acetate, 3-methyl-3 methylmethoxypentyl Methyl acetate, 3-methyl-4 monomethoxypentyl acetate, 4-methyl-4 to methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, Methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, 2-hydroxy-2-methyl-propionic acid Methyl ester, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl- 3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, '2-hydroxy-3 -Methyl methyl butyrate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, Methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate, benzyl methyl ether, benzyl ether, dihexyl ether, benzyl acetate, benzoin Ethyl Ester, Diethyl Oxalate, Diethyl Maleate, r-Butyrolactone, Benzene, Toluene The paper size is applicable to China National Standard (CNS) A4 (2i0x297 mm) " '-19- (Please read the precautions on the back before filling out this page)-_ Order _ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative, printed 1242689 A7 B7 V. Invention Description (17) (Please read the precautions on the back before filling out this page) , Xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerol and the like. These can be used alone or in combination of two or more. The amount of these solvents is, for example, a spin coating method to obtain a film thickness of more than 20 // m, preferably the solid content concentration in a chemically amplified negative photoresist composition for thick films. Can be in the range of 30% to 65% by weight. If the solid content concentration is less than 30% by weight, it will be difficult to produce a thick film suitable for the material for bump formation, and if it exceeds 65% by weight, the fluidity of the composition will be significantly deteriorated to make it difficult to handle, In addition, it is not easy to obtain a uniform resist film when the spin coating method is used. In addition to the foregoing components, the chemically amplified negative photoresist composition for thick films of the present invention may contain secondary or tertiary amines such as triethylamine, tributylamine, dibutylamine, triethanolamine, etc., if necessary. Quenching agent. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, in the chemically amplified negative photoresist composition for thick films of the present invention, in order to improve the adhesion to the substrate, an adhesion aid may not be used. The functional silane coupling agent is effective as the bonding aid used. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, an acrylic fluorenyl group, an isocyanate group, an epoxy group, and the like, and specific examples include trimethoxysilyl benzoic acid, r -Methacrylic acid propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, / 3-(3,4-epoxycyclohexyl ) Ethyltrimethoxysilane. The blending amount thereof is preferably not more than 20 parts by weight based on 100 parts by weight of the component (A). In addition, in the chemically amplified negative photoresist composition for thick film of the present invention, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -20-1242689 A7 B7 _____ V. Description of the invention (18) (Please read the precautions on the back before filling this page) For the sake of fine adjustment of the solubility of the alkaline phase solution, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isopropyl Monocarboxylic acids such as valeric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3- Monohydroxycarboxylic acids such as hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisoarsinic acid, syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid Acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4 monocyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, cyclohexane Polycarboxylic acids such as tetracarboxylic acid, butanetetracarboxylic acid, 1,2,5, 8-naphthalenetetracarboxylic acid; itaconic anhydride, glassyper anhydride, Citraconic anhydride, dodecene succinic anhydride, trimellitic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, heming anhydride, 1, 2, 3, 4-butanetetracarboxylic anhydride, Cyclopentanetetracarboxylic acid, Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumer Cooperatives, Printed anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic acid ester Anhydrides, glycerol, trimellitic anhydride, etc. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide may be added. Amine, N-methylpyrrolidone, dimethylasco, benzyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, caprylic acid, monooctanol, 1-nonanol, benzyl alcohol, benzyl acetate High boiling point solvents such as esters, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellulose acetate, etc. The amount of the aforementioned solvent is not particularly limited as long as it can be adjusted according to the application and coating method, and the composition is uniformly mixed, but the Chinese national standard (CNS) A4 specification (210X297 mm) is applied to the obtained paper size ) " ~ '-21-1242689 A7 B7_ 5. The composition of the invention description (19) is 60% by weight or less, preferably 40% by weight or less. The chemically amplified negative resist composition for thick films of the present invention may contain a colorant or the like as necessary. Examples of the colorant include constitutional pigments such as alumina white, clay, barium carbonate, and barium sulfate; zinc white, lead white, Huang Dan, Hong Dan, ultramarine, brilliant blue, titanium oxide, zinc chromate, iron red, and carbon Black and other inorganic pigments; bright carmine 6 B, permanent red 6 B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green and other organic pigments; basic dyes such as magenta and rhodamine Direct dyes such as direct bright red and direct orange; acid dyes such as rosin, m-amine yellow. These additives are in a range that does not impair the essential characteristics of the composition, and it is preferably 50% by weight or less with respect to the obtained composition. The thick-film chemically-amplified negative photoresist composition of the present invention is prepared by mixing and stirring only in accordance with ordinary methods. If necessary, a disperser such as a dissolver, a homogenizer, and a three-roll mill can be used to disperse or mixing. After mixing, filtration may be performed by using a mesh, a membrane filter, or the like. The composition of the present invention is suitable for coating as a thick film on a substrate, but its use range is not limited to this, but can also be used for etching various substrates such as copper, chromium, iron, and glass substrates. A protective film or a resist film for semiconductor manufacturing is used. The formation of bumps using the composition of the present invention as a thick film resist film is performed as follows. (1) Formation of coating film: A solution of the composition prepared in the above manner is coated on a substrate having a predetermined wiring pattern, and the solvent is removed by heating to form a required coating film. For the coating method on the substrate to be processed, spin coating method, roll coating method, screen printing method, thin-layer coating method, etc. can be adopted. ^ Paper size applies Chinese National Standard (〇 奶) 84 (210/297). (Mm) '~ ~ -22- (Please read the notes on the back before filling out this page) C. Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1242689 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 2. Description of the invention (20) Method. The pre-baking conditions of the coating film of the composition of the present invention vary according to the type of each component in the composition, the blending ratio, the thickness of the coating film, etc., but it is usually 130 ° C, preferably 80 to 120 ° C and about 2 to 60 minutes. (2) Radiation irradiation: The obtained coating film is irradiated with radiation, such as ultraviolet light or visible light having a wavelength of 300 to 500 nm, through a mask of a predetermined pattern, so that only the wiring patterns that will form bumps Partial exposure. These radiation sources can be low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, and the like. Here, radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, and electron rays. The amount of radiation varies depending on the type of each component in the composition, the blending amount, and the film thickness of the coating film, but it is, for example, 100 to 2000 mJ / cm2 when using an ultra-high pressure mercury lamp. (3) Heating: After exposure, heating is performed by a well-known method. (4) Revealing phase: The method of revealing phase after radiation irradiation is to use alkaline aqueous solution as the developing solution. It does not need to be dissolved and removed to make only the radiation irradiated portion remain. As the phase solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethyl Amine, dimethylethanolamine, triethanolamine, tetramethylammonium hydride, tetraethylammonium hydride, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene , 1,5-Diazabicyclo [4,3,0] -5-nonane and other alkali aqueous solutions. In addition, it can also be added to the above-mentioned alkali solution in an appropriate amount. The paper size applies the Chinese National Standard (CNS) A4 specification (210'〆 297 mm) (Please read the precautions on the back before filling this page)

-23- 1242689 A7 ___ B7 V. Description of the invention (21) Water solution containing methanol, ethanol and other water-soluble organic solvents or surfactants is used as the phase solution. (Please read the notes on the back before filling this page.) The appearance time varies according to the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but it is usually 1 to 30 minutes. The method may be any one of a liquid filling method, a dipping method, a kneading method, and a spray phase display method. After showing the phase, wash with water for 30 to 90 seconds and dry it with an air gun or oven. In addition, the plating method is not limited, and various conventionally known plating methods can be used. As the plating solution, a solder plating solution or a copper plating solution is preferably used. The film thickness obtained from the chemically amplified negative photoresist composition for thick films of the present invention is in the range of 20 to 150 / zm, preferably 30 to 120 // m, and more preferably 40 to 9 0 // m. If the film thickness is below 20 // m or above 15 0 // m, the performance required by the composition cannot be met. [Examples] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention will be specifically described below according to examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise noted, parts refer to parts by weight and% refer to% by weight. < (A) Synthesis of Alkali-Soluble Resin > Synthesis Example 1 M-cresol and p-cresol were mixed in a ratio of 60:40 by weight, and formaldehyde was added thereto, and an oxalic acid catalyst was used and the method was conventional. Condensation is performed to obtain a cresol novolak resin. This resin is treated separately to remove the low molecular weight paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -24-1242689 Α7 Β7 22 5. Description of the invention (domain, the weight average molecular weight is 1 0 0 0 0 phenolic lacquer resin. This resin is phenolic lacquer resin A 1. · -Pack-(Please read the precautions on the back before filling this page) Synthesis Example 2 Add formaldehyde water to m-cresol, An oxalic acid catalyst is used to perform condensation in accordance with a conventional method to prepare a m-cresol aldehyde resin. This resin is separately treated to remove the low-molecular area, and a phenol resin having a weight average molecular weight of 600 is obtained. It is phenolic lacquer resin A 2. Example 1 (a) 90 parts of phenolic lacquer resin A and (b) a hydroxystyrene homopolymer (Mw (molecular weight) 2500) (manufactured by Japan Soda Co., Ltd., product Name UP — 2500) 10 parts, (B) 0.5 part of acid generator represented by the following formula, (C) hexamethylene oxide melamine as crosslinker (manufactured by Sanwa Chemical Co., Ltd., Nicolak Mw— 1 〇〇) 10 parts dissolved in propylene glycol methyl ether acetate 1 50 After filtering in a solvent, a membrane filter with a pore diameter of 1.0 m was used to modulate the negative photoresist composition printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The composition was used for the characteristics evaluation as described below. Results As shown in Table 1. C4H9—S—'〇—N 〇2

〇—-S *** " '· 〇2 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -25-1242689 Α7 B7 5. Description of the invention (23) Example 2 will (a) The components were replaced with phenolic lacquer resin A 2, and the rest were operated in the same manner as in Example 1 to prepare a negative photoresist composition. Using this composition, the characteristics shown below were evaluated. The results are shown in Table 1. Example 3 In addition to (a) component and (b) component, (a) 50 parts of phenolic lacquer resin A2 and (b.) Hydroxystyrene homopolymer (M w 2 50 0 0) (Japan Except for 50 parts made by Cao Da Co., trade name u P-2 500), the rest were operated in the same manner as in Example 1 to prepare a negative photoresist composition. Using this composition, the characteristics described below were evaluated. The results are shown in Table 1. Example 4 The component (B) was changed to 1 part of ginseng (2,3-dibromopropyl) isocyanate, and the rest was performed in the same manner as in Example 1 to prepare a negative photoresist composition. Using this composition, the characteristic evaluation shown below was performed. The results are shown in Table 1. Example 5 The component (B) was changed to one part of the acid generator represented by the following formula, and the rest was operated in the same manner as in Example 2 to prepare a negative photoresist composition. Using this composition, the characteristic evaluation shown below was performed. The results are shown in Table 1. ^ Zhang scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm) '-26-(Please read the precautions on the back before filling out this page)). Packing. Order printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs 1242689 24

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (0

N—0—S—CR 0 Comparative Example 1 Except for (b) a homopolymer of hydroxystyrene, the rest of the shellfish [J was operated in the same manner as in Example 1 to prepare a negative photoresist composition. Using this composition, the characteristics shown below were evaluated. The results are shown in Table 2. Comparative Example 2 Instead of using (B) an acid generator and (C) a cross-linking agent, a compound represented by the following chemical formula (1) was used to make 1,2-naphthoquinonediazide-4 -sulfonamidine Except for 20 parts of the photo-initiated reaction initiator of the chlorine 2 mole reaction, the other was performed in the same manner as in Example 1 to prepare a negative photoresist composition. Using this composition, the characteristic evaluation shown below was performed. The results are shown in Table 2.

This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-27- 1242689 A7 B7 V. Description of the invention (25) Evaluation method of characteristics Compatibility (Please read the precautions on the back before filling out this page) Mix the aforementioned composition at room temperature and stir it for 1 2 hours to observe visually The state of dissolution immediately after stirring and 12 hours after the stirring. The evaluation of the dispersion state is performed according to the following evaluation criteria. ○: After stirring for 12 hours, it was visually confirmed that the composition was uniformly dispersed. △: The composition was dispersed uniformly after stirring for 12 hours, but phase separation occurred due to standing for a long time. X: The composition was not uniformly dispersed after stirring for 12 hours. Applicability Using a centrifugal spreader on a 5 inch silicon wafer, in the case of a coating film having a film thickness of about 20 // m, the composition was coated at 18,000 rpm for 25 seconds, and then Pre-baked on a hot plate for 6 minutes at 110 ° to form a thick film. In the case of a coating film with a thickness of about 6 5 // m, it is coated at 80 rpm for 25 seconds, and then prebaked on a hot plate at 110 ° C. 9 Staff of Intellectual Property Bureau, Ministry of Economic Affairs The consumer cooperative prints minutes to form a thick film. In the case of a coating film having a film thickness of about 1 2 0 # m, it was coated at 800 rpm for 2 5 seconds, and then prebaked on a hot plate at 1 10 ° C for 1 minute, and then baked at 8 0 After coating at 0 rpm for 25 seconds, pre-baking at 110 ° C for 1 minute, coating at 80 rpm for 2 5 seconds, and pre-baking at 11 ° C for 1 3 minutes to form Thick film. Secondly, through the pattern mask used for measuring the phase-resolving force, the paper size used by the stepper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -28- 1242689 A7 B7 V. Description of the invention (26) (please first Read the notes on the back and fill in this page) (stepper) (Ultra-high-tech company, Saturn 3-Wafer Stepper) Divide one coated substrate and divide it between 2000 and 300 m J The range of / c m2 performs stepwise ultraviolet exposure. After exposure, it was heated at 110 ° C. for 6 minutes, and the phase was developed with a phase-exhibiting liquid (trade name: PM ER series 歹! J, P-7 G, manufactured by Tokyo Applied Chemical Co., Ltd.). Thereafter, washing with flowing water was performed, and nitrogen gas was blown to obtain a patterned cured product. This was observed under a microscope, and the phase resolution was determined according to the evaluation criteria described below. 〇: 5 // m square hole pattern (hole pattern) was dephased by any of the foregoing exposure amounts, and no residue was recognized. X: 5 // The pattern of row holes in the four corners is not dephased, or a residue is recognized. At this time, the aspect ratio (aspect ratio) is also measured (aspect ratio = the height of the resist on the pattern + the width of the resist on the pattern). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs, printed the substrate with a pattern-like solid obtained in the "Evaluation of Phase and Phase Decomposition" as a test specimen, and then applied an oxygen plasma to honing processing , Immersed in a copper sulfite plating solution for 3 hours at 40 ° C, and washed with flowing water to obtain a treated sample. Use an optical microscope or an electron microscope to observe the state of the bumps and the pattern-like cured product formed on the specimen to be treated, and judge the resistance of the pattern-like cured product to the plating solution and the shape of the bumps according to the evaluation criteria described below. The resistance of the pattern-like cured product to the plating process. ○: The state of the formed bumps and the patterned cured product is not particularly changed and is good. The size of this paper is in accordance with Chinese National Standard (〇 奶) 8.4 Specification (2 丨 0 /; 297 mm) ~ -29- 1242689 A7 ________ B7 V. Description of the Invention (27) x · Cracks on the patterned solid , Bulging or chipping, or coarse sugar on the surface of the patterned hardened object. (Please read the precautions on the back before filling in this page) The shape of the bumps is the same as that of "Plating Resistance Evaluation", and the processed specimens are prepared, and the formed bumps and patterns are observed with an optical microscope or an electron microscope. The state of the solid cured product was determined based on the following evaluation criteria. If the bump shape is good, the angle between the substrate and the bump and the error ratio to the mask size are measured. ○: The shape of the bumps is good (depending on (following) the pattern-like cured product). X: The shape of the bumps does not depend on the patterned solidified substance, and bulging occurs. The Consumer Cooperative of the Intellectual Property Bureau of the Peeling Ministry of Economic Affairs printed a substrate with a pattern-shaped hardened body obtained in the "Evaluation of Phase and Phase Degradation" as a test specimen, and was immersed in a peeling solution with stirring at 70 ° C (Tokyo After 10 minutes in a stripper (7 1 0) manufactured by Applied Chemical Co., washing with a washing liquid with alcohol to peel off the pattern-like cured product, and visually observing or using an optical microscope were evaluated according to the following criteria. ○: Residues of the patterned cured product are not recognized. X: Residues of patterned solidified matter are recognized. Photosensitive film is formed on a 5-inch wafer with a film thickness of about 40 // m, and a pattern mask is used to measure the phase-resolving force, and a stepper (made by ultra-high-tech company, this paper size applies Chinese national standards) (CNS) A4 size (210 X 297 mm) -30- 1242689 A7 B7 V. Description of the invention (28) Saturn Spectrum 3-Wafer Stepper) Divide a coated substrate and divide it between 200 and 1 Stepwise ultraviolet exposure was performed in the range of 0 0 0 0 m J / cm2. This phase was developed using a phase display liquid (manufactured by Tokyo Applied Chemicals Co., Ltd. under the trade name P M E R series, P-7 G). It was then washed with running water and blown with nitrogen to obtain a patterned cured product. Observe the cured product with a microscope, and measure the 5 @ m four-corner hole pattern to dissolve the phase. The exposure of the residue is not recognized. (Please read the precautions on the reverse side before filling out this page) I · Print · Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Form 1, Example 2 3 4 5 Compatibility 〇 〇〇〇〇〇〇〇〇〇 Coating 〇〇〇〇〇〇〇〇 Film thickness (// m) 20 65 20 65 120 65 65 65 Phase apparent and dephasing property 0.000 Dimensions 2 1 3 3 3 2 1 3 Resistance to plating solution 〇 〇〇〇〇〇〇 Bump shape 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ００００００００００００００００００００００００００ feeling China National Standard (CNS) A4 specification (210X 297 mm) -31-1242689 A7 B7 V. Description of the invention (29) || 2 Table __ Comparative Example 1 2 Compatibility 〇〇 Coatingability 〇〇film thickness (# m) 65 6 5 Phase appearance and phase dissociation XX aspect ratio 2 > 1 Resistance to plating solution. ○ Bump shape 〇X Peelability 〇 Sensitivity fm J / cm2) 1000 1000 (Note) Sensitivity of Comparative Example 2 Significantly poor sex. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Effects of Invention] The present invention can provide high sensitivity and good plating resistance, and can be used as a CSP manufacturing technology Bumps, rewiring, and metal pillar forming materials are suitable for thick film chemically amplified negative photoresist compositions for thick films, photoresist substrates, and methods for forming bumps using the same. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -32-

Claims (1)

1242689 A8 B8 C8 D8 ", patent application scope j 1 · A chemically amplified negative photoresist composition for thick film, which contains (A) an alkali-soluble resin, (B) a compound that generates an acid due to radiation, and (C) A compound that undergoes a cross-linking reaction in the presence of an acid, characterized in that the aforementioned (A) component consists of (a) a phenolic lacquer resin having a weight average molecular weight in the range of 5000 to 10,000, and (b) at least It is a mixture of polymers having a hydroxystyrene structural unit and a weight average molecular weight of less than 5000. 2 _ For example, the chemically amplified negative photoresist composition for thick films of the scope of patent application item 1, wherein ( a) The composition is in the presence of an acid catalyst / made from a cresol novolak resin obtained by condensing m-cresol with aldehydes. 3 · If the scope of the patent application for item 1 of the thick film is used for chemical amplification Type negative photoresist composition, in the (A) component, if the sum of the (a) component and (b) component is 100 parts by weight, the (a) component is 50 to 98 parts by weight, ( b) the composition is 50 to 2 parts by weight. Item of chemically amplified negative photoresist composition for thick film, wherein (B) component has at least two in general formula RS〇20-N = C (CN)-(where R is substituted or unsubstituted) Alkyl or aryl) compounds represented by oxime sulfonic acid groups. 5 · For example, the chemically-amplified type [type photoresist composition for thick film] of thick film for item 4 of the scope of patent application, in which the component (B) is represented by the general formula R—S〇2〇—N = C (CN) —A —C (CN) —〇S〇2 —R (where A is a binary organic group, and R is a substituted or unsubstituted alkyl group or Fangji) The paper size of the table applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) 1242689 A8 B8 C8 D8 VI. The compound indicated in the scope of patent application 2. 6 · The chemically amplified negative photoresist composition for thick film as described in the scope of patent application No. 5 in which, in the general formula of component (B), A is phenyl group and R is lower alkyl group. 7 · As in the scope of patent application No. 1 for thick film chemically amplified negative photoresistor group When the sum of (A) component, (B) component, and (C) component is 100 parts by weight, (B) component is 0.1 to 1 part by weight. 8 · —A kind of photoresist substrate , Is a negative type photoresist substrate with a substrate and a negative type photoresist layer provided on the substrate, and is characterized in that the aforementioned negative type photoresist layer is any one of the first to seventh items in the scope of patent application The thick film of the item is made of chemically amplified negative photoresist composition and has a film thickness of 20 to 15 0 // m. 9 · A bump forming method, characterized in that: a chemically amplified negative photoresist composition for thick films according to any one of the scope of patent applications Nos. 1 to 7 is coated on the base material of an electronic component, A selective exposure, heat treatment, and development treatment are sequentially applied to the obtained coating film to form a negative-type resist film pattern, and then the resist film pattern is subjected to plating treatment as a mask. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) Binding and Ordering Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -34-